Odd-number cyclo[n]carbons sustaining alternating aromaticity

Odd-number cyclo[n]carbons sustaining alternating aromaticity

Cyclo[n]carbons (n = 5, 7, 9,..., 29) composed from an odd number of carbon atoms are studied computationally at density functional theory (DFT) and ab initio complete active space self-consistent field (CASSCF) levels of theory to get insight into their electronic structure and aromaticity. DFT cal...

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Bibliographic Details
Published in:The Journal of Physical Chemistry A Vol. 126, № 16. P. 2445-2452
Other Authors: Baryshnikov, Gleb V., Valiev, Rashid R., Valiulina, Lenara I., Kurtsevich, Alexandr E., Kurtén, Theo, Sundholm, Dage, Pittelkow, Michael, Zhang, Jinglai, Ågren, Hans
Format: Article
Language:English
Subjects:
циклоуглероды
теория функционала плотности
электронная структура
ароматичность
статьи в журналах
Online Access:http://vital.lib.tsu.ru/vital/access/manager/Repository/koha:001001601
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245 1 0 |a Odd-number cyclo[n]carbons sustaining alternating aromaticity  |c G. V. Baryshnikov, R. R. Valiev, L. I. Valiulina [et al.] 
336 |a Текст 
337 |a электронный 
504 |a Библиогр.: 60 назв. 
520 3 |a Cyclo[n]carbons (n = 5, 7, 9,..., 29) composed from an odd number of carbon atoms are studied computationally at density functional theory (DFT) and ab initio complete active space self-consistent field (CASSCF) levels of theory to get insight into their electronic structure and aromaticity. DFT calculations predict a strongly delocalized carbene structure of the cyclo[n]carbons and an aromatic character for all of them. In contrast, calculations at the CASSCF level yield geometrically bent and electronically localized carbene structures leading to an alternating double aromaticity of the odd-number cyclo[n]carbons. CASSCF calculations yield a singlet electronic ground state for the studied cyclo[n]carbons except for C25, whereas at the DFT level the energy difference between the lowest singlet and triplet states depends on the employed functional. The BHandHLYP functional predicts a triplet ground state of the larger odd-number cyclo[n]carbons starting from n = 13. Current-density calculations at the BHandHLYP level using the CASSCFoptimized molecular structures show that there is a through-space delocalization in the cyclo[n]carbons. The current density avoids the carbene carbon atom, leading to an alternating double aromaticity of the oddnumber cyclo[n]carbons satisfying the antiaromatic [4k+1] and aromatic [4k+3] rules. C11, C15, and C19 are aromatic and can be prioritized in future synthesis. We predict a bond-shift phenomenon for the triplet state of the cyclo[n]carbons leading to resonance structures that have different reactivity toward dimerization. 
653 |a циклоуглероды 
653 |a теория функционала плотности 
653 |a электронная структура 
653 |a ароматичность 
655 4 |a статьи в журналах 
700 1 |a Baryshnikov, Gleb V. 
700 1 |a Valiev, Rashid R. 
700 1 |a Valiulina, Lenara I. 
700 1 |a Kurtsevich, Alexandr E. 
700 1 |a Kurtén, Theo 
700 1 |a Sundholm, Dage 
700 1 |a Pittelkow, Michael 
700 1 |a Zhang, Jinglai 
700 1 |a Ågren, Hans 
773 0 |t The Journal of Physical Chemistry A  |d 2022  |g Vol. 126, № 16. P. 2445-2452  |x 1089-5639 
852 4 |a RU-ToGU 
856 4 |u http://vital.lib.tsu.ru/vital/access/manager/Repository/koha:001001601 
908 |a статья 
999 |c 1001601  |d 1001601 

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